The Composition of Crude Corn Oil Recovered after Fermentation via Centrifugation from a Commercial Dry Grind Ethanol Process

A study was conducted to examine the chemical composition of corn oil obtained after fermentation of corn to make fuel ethanol via centrifugation and compare its composition to that of corn germ oil (commercial corn oil) and experimental corn oils. The levels of free fatty acids in the post fermentation corn oil were high (11–16%), as previously reported. The levels of free phytosterols and hydroxycinnamate steryl esters (similar to oryzanol in rice bran oil) were higher than those of corn germ oil and were comparable to those of ethanol-extracted corn kernel oil. The levels of tocopherols were lower in post-fermentation oil than in either corn germ oil or ethanol extracted corn kernel oil. The levels of lutein and zeaxanthin in post-fermentation were much higher than those in corn germ oil and were comparable to those in ethanol-extracted corn kernel oil. Overall, exposure to all upstream processes of a fuel ethanol plant, including high-temperature liquefaction, saccharification and fermentation appeared to have the most notable effect on tocopherols, but it had little effect on the levels of free phytosterols, hydroxycinnamate steryl esters, lutein and zeaxanthin. It may be desirable to recover these valuable functional lipids prior to using the post-fermentation corn oil for industrial applications such as making biodiesel if a cost-effective recovery process can be developed.     

The composition of corn oil obtained by the alcohol extraction of ground corn

All commercial corn oil is obtained by the hexane extraction of corn germ. The chemical composition of commercial corn oil has been well characterized. This study was under-taken to quantitatively evaluate the lipid composition of corn oil obtained by the ethanol extraction of ground, whole corn kernels. When corn oil was obtained by extracting ground corn kernels (ground corn) with polar or nonpolar solvents, the resulting corn oil contained much higher levels of hydroxycinnamate steryl esters (≈0.3%) than those found in commercial hexane-extracted corn (germ) oil (≈0.02%). The levels of valuable tocopherols and tocotrienols were also significantly higher in kernel oil than in traditional corn germ oil. We previously reported that when corn oil was obtained by extracting corn kernels with polar solvents, the oil contained two polyamine conjugates, diferuloylputrescine and p-coumaroyl feruloylputrescine. In the current study, when ground corn was extracted with ethanol, the resulting corn oil contained about 0.5% diferuloylputrescine and about 0.2% p-coumaroyl feruloylputrescine. This is the first study to quantify these unique compounds in corn oil extracted by new techniques. This compositional information is important because this new oil is being considered for human food use.     

Surfactant-Based Oil Extraction of Corn Germ

An aqueous surfactant-based extraction system was developed for the extraction of corn oil from corn germ with anionic extended surfactants. The surfactants used in this study were sodium linear-alkyl polypropoxylated polyethoxylated sulfates (C_12,14–P₁₀–E₂–SO₄Na and C₁₀–P₁₈–E₂–SO₄Na). Interfacial tension, critical microemulsion concentration (CμC), and optimum salinity values of the extended surfactants with corn oil were determined. In the extraction process, the ground corn germ was shaken with predetermined surfactant and salt concentrations at room temperature for 45 min. About 83%, the sum of total free oil and total oil-in-water emulsion, of the corn oil was extracted from the corn germ using a formulation of 0.4% C_12,14–P₁₀–E₂–SO₄Na and 1% NaCl. A solid/liquid ratio of 1/10 performed best for efficient oil recovery. The chemical compositions of the extracted corn oils were found to be similar to that of hexane extracted corn oil.     

Using Microwave Heating and Microscopy to Estimate Optimal Corn Germ Oil Yield with a Bench-Scale Press

The increase in ethanol production from corn has prompted development of processes to separate corn germ. The corn germ co-product would be a source of corn oil if a practical oil separation process were also developed. We carried out bench-scale corn-germ-pressing experiments to determine the maximum potential oil recovery which were then used to estimate commercial germ crushing costs. Corn germ was preheated in a microwave oven and oil was then extracted with a bench-scale press. Preheating the germ was necessary to obtain good oil yields. The uniform heating of the microwave oven more closely resembles compressive heating of commercial scale presses than does oven heating. Three different microscopic techniques were used to examine the effects of microwave and conventional-oven heating on corn germ. Microscopy revealed that microwave heating heated oil in the germ more quickly than the other components of the germ. Heating by both methods destroyed lipid body membranes and oil coalesced and pooled. Less oil could be pressed from germ initially containing 3–6% moisture than germ containing 15–20% moisture. Maximum oil recovery of about 65% was obtained for all germs tested when the optimum press temperature and germ feed moisture were used. Mention of trade names or commercial products in this publication is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the US Department of Agriculture.     

A Process for the Aqueous Enzymatic Extraction of Corn Oil from Dry Milled Corn Germ and Enzymatic Wet Milled Corn Germ (E-Germ)

A bench-scale aqueous enzymatic method was developed to extract corn oil from corn germ from either a commercial corn dry mill or corn germ from a newly-developed experimental enzymatic wet milling process (E-Germ). With both types of germs, no oil was extracted when acidic cellulase was the only enzyme used. Pre-treating dry milled corn germ by heating it in boiling water or microwave pretreatment, followed by enzymatic extraction with the acidic cellulase resulted in oil yields of about 43% and 57%, respectively. A two-step process, combining both acidic cellulase and alkaline protease treatments, with no heat pretreatment, achieved oil yields of 50–65% from dry milled corn germ and 80–90% from E-Germ. Mention of trade names or commercial products in this publication is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture.     

A comparison of commercial enzymes for the aqueous enzymatic extraction of corn oil from corn germ

An aqueous enzymatic method was developed to extract corn oil from corn germ. The basic steps in the method involved “churning” the corn germ with various enzymes and buffer for 4 h at 50°C, and an additional 16 h at 65°C, followed by centrifugation and removal of the oil layer from the surface. No hexane or other organic solvents are used in this process. By using oven-dried corn germ samples (6 g) from a commercial corn wet mill, corn oil yields of about 80% were achieved using three different commercial cellulases. A fourfold scale-up of the method (to 24 g of germ) resulted in oil yields of about 90%. Nine other commercial enzymes were evaluated and resulted in significant but lower oil yields. In the absence of enzymes, oil yields of 27 to 37% were achieved. The chemical compositions of hexane-extracted vs. aqueous enzymatic-extracted corn oils were very similar.     

Fatty Acid,Phytosterol, and Polyamine Conjugate Profiles of Edible Oils Extracted from Corn Germ,Corn Fiber,and Corn Kernels

This study compared the profiles of fatty acids, phytosterols, and polyamine conjugates in conventional commercial corn oil extracted from corn germ and in two “new-generation” corn oils: hexane-extracted corn fiber oil and ethanol-extracted corn kernel oil. The fatty acid compositions of all three corn oils were very similar and were unaffected by degumming, refining, bleaching, and deodorization. The levels of total phytosterols in crude corn fiber oil were about tenfold higher than those in commercial corn oil, and their levels in crude corn kernel oil were more than twofold higher than in conventional corn oil. When corn kernel oil was subjected to conventional degumming, refining, bleaching, and deodorization, about half of the phytosterols was removed, whereas when corn fiber oil was subjected to a gentle form of degumming, refining, bleaching, and deodorization, only about 10% of the phytosterols was removed. Finally, when the levels of polyamine conjugates (diferuloylputrescine and p-coumaroyl feruloylputrescine) were examined in these corn oils, they were only detected in the ethanol-extracted crude corn kernel oil, confirming earlier reports that they were not extracted by hexane, and providing new information that they could be removed from ethanol-extracted corn kernel oil by conventional degumming, refining, bleaching, and deodorizing.     

Foam Separation of Oil from Enzymatically Treated Wet-Milled Corn Germ Dispersions

More than 9 billion gallons of ethanol were produced in 2008, mostly from dry grind corn fermentation plants. These plants are a potential source of substantial amounts of corn oil, if an economical method of separating it can be developed. In this work, oil was separated from corn germ by aqueous enzymatic extraction (AEE). Batches of wet-milled corn germ in water were preheated in a pressure cooker, ground in a colloid mill, and churned in a vertical column/mixing vessel system, after the addition of enzyme. Nitrogen gas was then bubbled through the column removing an overflowing foam fraction which was subsequently centrifuged to separate free oil. Using a newly commercialized enzyme complex it was found that 80% of the oil could be recovered using a w/w ratio of enzyme solution to germ of 1:80. The low dose and low price of the enzyme complex leads to a cost estimate of AEE of corn oil from germ, similar to the wet-milled germ extracted, cost competitive with expelled oil (with the separation and drying of the foam protein), and feasible for commercialization in a dry grind plant retrofitted to separate germ.     

Antioxidant Activity of Oat Malt Extracts in Accelerated Corn Oil Oxidation

Oat cultivar AC Vermont was malted to concentrate antioxidants, milled to fractionate only the endosperm portion and extracted with methanol to isolate the crude antioxidants. The oat malt antioxidant fraction was assessed as a natural antioxidant based upon enhancing the stability of corn oil against oxidation and compared to the synthetic antioxidant butylated hydroxytoluene (BHT). The induction time (time required for the formation of 10 meq hydroperoxide per kilogram corn oil thermally oxidized) was used to measure antioxidant activity of oat antioxidant or BHT. The protection factor achieved by crude oat malt antioxidant extract concentrate at 0.26% (2,600 μg/g) was comparable to BHT (75 μg/g). The antioxidant activity of the oat and barley malt extract concentrates was not significantly different. However, the extract concentrate of oat malt had 44% less color compared to that of barley malt at equal concentrations showing its potential as a natural food antioxidant.     

Antioxidant Activity of Raisin Extracts in Bulk Oil,Oil in Water Emulsion,and Sunflower Butter Model Systems

The antioxidant activities of the raisin extract (RE) in stripped corn oil, stripped corn oil emulsions, and sunflower butter stored at 60 °C for up to 15 days was evaluated. Peroxide values and hexanal content were measured on a half day, 2 or 3 day basis for the emulsion, sunflower butter, and bulk oil, respectively. The RE had the best antioxidant activity in the bulk oil system. Statistical contrasts indicated the oxidation of bulk corn oil treated with RE was significantly (p < 0.001 and p = 0.044) lower than bulk oil and bulk oil treated with tertiary-butylhydroquinone (TBHQ), respectively. No differences (p = 0.15) in hexanal concentrations were observed in stored bulk oils treated with RE and TBHQ. However, both these materials inhibited hexanal formation better (p < 0.001) when compared to the control corn oil. In contrast, 200 μg/g TBHQ had better (p = 0.0004) antioxidant activity than 3,000 μg/g RE in the oil in water(o/w) emulsion. No significant differences (p = 0.1637) in hexanal formation were observed in the emulsions treated with RE and TBHQ. However, the data indicated that the RE treated emulsion did undergo more secondary oxidation than the emulsion treated with TBHQ beyond 110 h. The 3,000 μg/g RE had antioxidant activity in sunflower butter, but was less effective than the 200 μg/g TBHQ and a lower RE concentration (200 μg/g). The observations supported the hypothesis that RE has antioxidant activity in the multiple model systems.     

超临界CO2萃取玉米胚芽油工艺的研究

本文研究采用超临界ＣＯ２从玉米胚芽中萃取油品的工艺条件，运用响应面法探讨了萃取压力、萃取温度和物料粒径在油品产率为９０％时对ＣＯ２消耗量的影响，确定了最佳工艺参数，分析比较了超临界ＣＯ２萃取、正己烷索氏萃取和压榨三种方法对油品质量和脂肪酸组成的影响。     

Factors affecting oil extraction/water adsorption in sequential extraction processing of corn

The sequential extraction process (SEP) uses ethanol to extract oil and protein from cracked, flaked, and dried corn, and the dried corn simultaneously dehydrates the ethanol. Value-added co-products are possible, potentially making production of fuel ethanol more economical. The effects of solvent-to-corn (S/C) ratio, corn moisture content (MC), and number of extraction stages on ethanol drying, oil recovery, and protein loss during the simultaneous oil extraction/water adsorption step of SEP were evaluated. Extractions were carried out by using both aqueous ethanol and ethanol/hexane blends at 56°C. The S/C ratios tested were 3∶1, 2∶1 (control), 1.5∶1, and 1∶1 (w/w). More anhydrous ethanol, greater oil yields, and less co-extracted protein were obtained with higher S/C ratios. Less anhydrous ethanol and lower moisture adsorption capacities were obtained when the corn MC was ≥1.12%. Oil yields gradually decreased with drier corn, whereas protein loss increased when corn MC was <1.12%. Reducing the number of extraction stages from seven (original SEP) to five did not affect ethanol drying capability, oil yields, and protein co-extracted with oil. Using ethanol/hexane blends resulted in more anhydrous ethanol, higher oil yields, and less protein co-extracted with oil.     

Physical and Chemical Processes to Enhance Oil Recovery from Condensed Corn Distillers Solubles

Oil recovery from corn fermentation co-products can provide feedstock for biodiesel production. The effects of physical and chemical processes on oil recovery from condensed corn distillers solubles (CCDS) were investigated. Heating disrupted physical interactions in the CCDS and increased oil recovery by 2.5-fold when temperature was increased from 25 to 59 °C. Oil recovery at acidic pH conditions was significantly greater than at alkaline pH. Oil recovery at alkaline pH was increased by heating and addition of the reducing agent, sodium metabisulfite. Oil extraction using polar solvents isopropanol and butanol achieved greater than 80% oil recovery. When oil was co-extracted with zein using hexane and ethanol as co-solvents, the greatest total oil recovery was achieved, 89%. Churning CCDS at pH 3.5, 50 °C for 3 h achieved up to 80% oil recovery. This study provides data for designing further effective methods for oil separation from corn ethanol co-products.     

Extraction of oil from ground corn using ethanol

Corn oil was extracted from whole ground corn using ethanol as the solvent. The yield of oil was measured as a function of temperature, time of extraction, solvent-to-solids ratio, and ethanol concentration. Optimal conditions were a solvent-to-solids ratio of 4 mL/g corn, an ethanol concentration of 100%, 30 min of extraction time, and a temperature of 50°C. Under these conditions, a single batch extraction yielded ≈3.3 g oil/100 g corn, equivalent to 70% extraction efficiency. A three-stage extraction, where the same corn was exposed to fresh ethanol, resulted in a yield of ≈4.5 g/100 g corn (2.5 lb/bu of corn), equivalent to 93% recovery of the oil in corn. When anhydrous ethanol was used to repeatedly extract fresh corn, moisture was absorbed linearly by ethanol from the corn in successive stages, which, in turn, decreased oil yield and increased nonoil components in the extract.     

The influence of moisture content and cooking on the screw pressing and prepressing of corn oil from corn germ

Samples of corn germ were obtained from a commercial corn wet mill (factory dried to about 3% moisture) and a commerical corn dry mill (undried, produced in the mill with about 13% moisture). The germ samples (200 g each) were cooked for various times in either a conventional oven at 180°C or a microwave oven at 1500 W. Bench-scale single screw pressing was then performed. With the dry milled corn germ, no oil was obtained from the uncooked germ. A maximal yield of about 5% oil [26% of total oil recovery (TOR), relative to hexane extraction] was obtained by cooking the dry-milled germ for 6.5 min in a conventional oven at 180°C before pressing. A maximal yield of about 7% oil (37% TOR) was obtained by cooking the dry-milled germ for 4.5 min in a microwave oven at 1500 W before pressing. With the wet-milled germ, yields of about 7% oil (18% TOR) were obtained with the uncooked germ and yields increased to a maximum of about 22% oil (56% TOR) by cooking in a conventional oven at 180°C for 5 min or a maximum of about 17% oil (44% TOR) by cooking for 4 min in a microwave oven at 1500 W. These results indicate that microwave and conventional oven cooking are both effective pretreatments before pressing. Microwave preheating resulted in higher oil yields with dry-milled germ, and conventional oven pretreatment resulted in higher oil yields with factory-dried wet-milled corn germ.     

Composition and economic comparison of germ fractions from modified corn processing technologies

Several new processes for milling corn have been developed recently specifically to isolate germ as a value-added co-product and improve the profitability of dry-grind ethanol production. The present work used modified and conventional corn milling technologies to recover germ fractions from corn kernels using either wet or dry separation processes. This study determined the quality, composition, and yield differences among the corn germ produced and compared these properties with those of the conventional wet- and dry-milled germ. A method for calculating the estimated market value for germ produced by the alternative processing methods is given. There were significant differences in the oil, protein, starch, and ash compositions and in the estimated market values among germ fractions produced by the alternative milling processes. The different germ fractions produced (including the traditional wet-and dry-milled) were found to contain 18–41% oil, 13–21% protein, and 6–21% starch, depending on the milling process used. The estimated value of germ from these processes varied from as low as $0.058/lb ($0.128/kg) to a maximum of $0.114/lb ($0.251/kg), showing that the specific process used to produce the germ will have the major impact on the overall economics of the ethanol process.     

Analysis of free malondialdehyde in photoirradiated corn oil and beef fat via a pyrazole derivative

Malondialdehyde (MA) formed in linolenic acid, linoleic acid, corn oil and beef fat upon photoirradiation was determined by gas chromatography (GC). The MA produced was reacted with methylhydrazine to give 1-methyl-pyrazole and was subsequently analyzed on a GC equipped with a nitrogen-phosphorus specific detector and a fused silica capillary column. MA values determined by this method correspond to free or unbound MA levels. Linolenic and linoleic acids produced 867 μg MA/g and 106 μg MA/g, respectively. Oleic and stearic acids did not produce detectable levels of MA upon photoirradiation. Amounts of MA produced after eight hour irradiations of corn oil and beef fat were 56.24 μg/g and 25.01 μg/g, respectively. Some photoreaction products in irradiated corn oil also were identified as methylhydrazine derivatives.     

A Novel Method for the Production of Biodiesel from the Whole Stillage-Extracted Corn Oil

The extraction of corn oil from whole stillage and condensed distillers’ solubles (CDS) with hexane and its conversion to biodiesel were investigated. The analysis of the extracted oil showed 6–8 wt.% free fatty acid (FFA) in this oil. Acid, base, acid–base, and acid–base catalyzed transesterifications with intermediate neutralization with anion exchange resin were investigated. Experiments were performed with model corn oil substrates which contained 1.0–6.0 wt.% FFA. The effect of catalyst at 0.50–1.25 wt.% was studied at a 1:8 oil/methanol molar ratio. At 6.0 wt.% FFA concentration, the acid-catalyzed scheme was slow and resulted in less than 20% yield after 4 h, while the base-catalyzed was mostly consumed by the FFA and very little conversion was achieved. The acid–base catalyzed scheme succeeded in reducing the FFA content of the oil through the acid-catalyzed stage, and yields in excess of 85% were achieved after the second stage of the reaction with a base catalyst. However, formation of water and soap prevented the separation of product phases. An alternative acid–base catalyzed scheme was examined which made use of a strong anion exchange resin to neutralize the substrate after the initial acid-catalyzed stage. This scheme resulted in the effective removal of the acid catalyst as well as the residual FFA prior to the base-catalyzed stage. The subsequent base-catalyzed stage resulted in yields in excess of 98% for a 7.0 wt.% FFA corn oil and for the corn oil extracted from CDS.     

Enzyme Treatments to Enhance Oil Recovery from Condensed Corn Distillers Solubles

The objective of this study was to determine the effect of enzyme hydrolysis of various corn components on oil recovery from condensed corn distillers solubles (CCDS). Hydrolysis with a commercial protease significantly increased oil recovery as the enzyme concentration increased, with the greatest oil recovery being 70% at 10% v/w (dry weight basis) enzyme concentration. Increasing centrifugal force from 8,500 to 12,240×g was only slightly effective for the non-enzyme treated samples. Reducing CCDS particle size by grinding with a mortar and pestle increased oil recovery to 83% when an enzyme combination of a commercial cellulase mixture and a protease was used. Particle size reduction of CCDS by high-speed blending resulted in low oil recovery, but the oil recovery was significantly improved after enzyme treatment. Zein-lipid interaction was very strong when tested in a model system, with only 10% of the oil being freed by centrifugation alone. Following enzyme hydrolysis of the zein-oil complex with a protease, oil recovery was increased to 97%. Overall, enzyme hydrolysis and further particle size reduction showed a small, albeit statistically significant, effect in increasing oil recovery from CCDS. These small increases may not justify the use of enzymes or processing modifications to reduce particle size in the ethanol industry, nonetheless, these data may provide a reference or insight to design more effective treatments for oil recovery.     

Changes in Lipid Composition During Dry Grind Ethanol Processing of Corn

During the dry grind ethanol process, ground corn is fermented and the major co-product is a feed called distillers dried grains with solubles (DDGS). This study investigated the changes that occur in the composition of corn oil that can be extracted from various process fractions during the dry grind ethanol process. In the first part of this study, samples of distillers dried grains, thin stillage, condensed distillers solubles (also known as syrup), and DDGS were obtained from 7 dry grind ethanol plants. The levels of deleterious free fatty acids were high (>7%) and those of valuable total phytosterols were also high in all fractions (>2%). In the second part of this study, changes in the content and composition of the fatty acids, phytosterols, tocopherols and tocotrienols were quantitatively analyzed in crude oil samples extracted from nine dry grind process fractions from three commercial ethanol plants. Fatty acid and phytosterol composition remained nearly constant in all nine fractions, although some significant variations in phytosterol composition existed among the fractions. Examination of the tocopherols and tocotrienols revealed that γ-tocopherol was the most abundant tocol in ground corn but an unknown tocol became the predominant tocol after fermentation and persisted in the remaining processing fractions and in the final DDGS product. Overall, the remaining majority of tocols remained relatively unchanged.